its never really blatantly stated when exactly willow became a full-fledged witch. her first spell was during season two when she tried to summon angel's soul. and in season three, when Buffy comes back, willow mentions that she's been dabbling in witchcraft. so...season two, episode 21 becoming part 1.
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She is "evil Willow" for the last three episodes of season six; Episode 20: Villains, Episode 21: Two To Go, Episode 22: Grave.
She uses magic.
Alyson Haningan
no.real spells are wiccan.
its a slow process...there was never an episode where willow was just kinda 'I'm gay' but the episode where she comes out to Buffy is season 4 episode 19 "New Moon Rising" the first episode you see Tara, which may be the episode where willow "goes gay" is season 4 episode 10 "Hush" you don't see willow's first gay kiss, however, until season 5 episode 16 "The Body"